Protein solution and new protein derivative and process of making same



Patented Feb. 6, 1934 UNITED STATES PATENT OFFICE PROTEIN SOLUTION ANDNEW PROTEIN DERIVATIVE AND PROCESS OF MAKING SAME I Charles Graenacher,Basel, Switzerland, assignor to Society of Chemical Industry in Basic,Basel,

Switzerland No Drawing. Application January 4, 1932, Serial No. 584,757,and in Switzerland January 27,

21 Claims. (Cl. 106-38) nary ammonium salts for themselves or in pres--ence of suitable liquids have the surprising property of dissolvingcellulose with the formation of solutions of more or less viscosity.Such liquids are above all anhydrous nitrogen-containing bases, such asanhydrous ammonia, or organic bases which do not decompose thequaternary ammonium salts, such as alkylamines (for example mono-, diortrimethylamine), aniline,

monomethylaniline, dimethylaniline, pyridine,

picoline, lutidine, technical pyridine bases, mixtures of thesecompounds, etc.

Among the ammonium salts the halides, such as the chlorides, bromides,and iodides are the most suitable. There may also be used other salts,such as for example sulfates, nitrates or organic salts, such asformates, acetates, etc. Among the ammonium salts particularly those arefurther suitable which derive from halogen hydracid ridinium chloride,preparedby heating together esters which contain up to 8 carbon atoms,such as benzyl chloride, chlorobenzyl chloride, ethyl, propyl or butylchlorideeor also from hexyl halides and octyl halides. Useful resultsmay however also be obtained with other halides, such as for examplewith esters of halogen containing fatty acid, such as chloracetic esteror unsaturated products, such as allyl halides,

The present invention is based on the observation that proteins, thisterm also comprising the protein-like degradation products of theproteins, such as albumoses and peptones, also possess the property ofdissolving in the aforesaid addition or ammonium compounds to yieldsolutions which contain the protein material in a very reactive form.According to the nature of the protein the dissolving temperature mustbe chosen more or less high. The solubility of the proteins may also beincreased by partial degradation,

which, as is'well-known, may be performed in various manners, forexample by preliminary treatment with acids, bases, sodium sulfide, andthe like. The solutions may be applied to the production of formedarticles or for the manufacture of further protein derivatives; forexample,

the dissolved proteins may be converted with extraordinary ease into newprotein derivatives by treatment with acidylating agents.

It has also been discovered that the new protein solutions have theproperty of mixing in any desired proportion with the solutions ofcellulose obtainable as described in U. S. patent application Serial No.563,218 with the formation of homogeneous solutions capable of improvedtechnical application. The mixed solutions may be applied for example,like the solutions described in the aforesaid specification, for themanufacture of formed objects, such as threads, films or artificialmasses, which may differ completely both in their physical propertiesand in their behavior towards dyestuffs from the products of theaforesaid patent application. Intimate mixtures of derivatives ofproteins and cellulose are furthermore obtained, for example, bytreating the mixed solutions with acidylating agents.

Of course, mixtures may also be obtained by dissolving the cellulose andthe protein simultaneously or successively in either order in anaddition product of an alkylating agent and a tertiary base.

The following examples illustrate the invention, the parts being byweight:-

Example 1 Into a mixture of pyridine and benzyl-py- 100 parts of drypyridine and parts of benzylchloride at 100-110 0., are introduced 10parts of dry,.finely powdered casein andthe mixture is stirred for about1 hour at 95 C. Casein dissolves with the formation of. a faintly milkysolution. The casein solution thus obtained may be used as an additionto a cellulose solution obtainable as described in U. S. patentapplication Serial No. 563,218, whereby there may be made spun materialshaving modified physical and dyeing properties; or the casein in theform of its solution may be subjected very easily to further chemicalreactions. Similar results are obtained with other proteins, forexample, with an acidyl casein such as acetyl casein.

Example 2 10 parts of dry finely powdered casein are introduced, whilststirring, into a mixture of '70 parts of ethyl pyridinium chloride and35 parts of pyridine at the temperature of the water-bath and themixture is maintained for 1 hour at this temperature with constantstirring.

The thick syrupy solution of the casein so obtained is allowed to coolto 80 C. and there are then introduced in small portions 10 parts ofbenzoyl chloride, stirring being continued. After the addition ofeachportion of benzoyl chloride, the mixture partially gelatinizes, butreverts to the form of a homogeneous viscous solution on furtherstirring. After the whole of the benzoyi chloride has been added themass is stirred for a further hour at 0., whereby there is obtained aviscous solution which can be drawn into threads; by allowing thesolution to flow into a suitable precipitating liquid, such as water,alcohol, etc., the benzoylated material must be precipitated in anydesired coherent form, for example in the form of small ribbons,threads, etc.

Example 3 l "12 parts of lintors and 1.5 parts of boiled-out tussoresilk in the form of small clippings are si-' multaneously dissolved in amixture of 150 parts of ethyl pyridinium-chloride and '75 parts ofpyridine, the dissolution occupying about 2 hours at C. There isobtained a highly viscous solu tion of cellulose and silk; it is capableof being spun and yields'a fibrous material which hardly differs fromnatural silk in its behaviour on dye ing. s

It will be understood that the natural silk solution may also be madeseparately and only then added to the cellulose solution. So also theremay be used 'instead of unaltered natural silk for producing a suitablesolution one of its cohversion products, obtainable in known manner byreprecipitation of the silk from a mineral acid or from a salt solution.

Example 4 i 50 parts of keratin (wool, feathers, hair, horn, etc.) areintroduced at ordinary temperature into 500 parts of a solution ofsodium sulfide (No.28) of 10 per cent strength and the mixture isallowed to stand for 24 to 36 hours with frequent stirring, whereby thekeratin dissolves practically completely. "After the solution has beenfiltered to remove undissolved matter, it is treated with acetic acid,whereby keratin-sulfolysate is precipitated in practically white form;it is filtered by suction, washed and dried and if necessary freed fromsulfur by extraction with car-- bon bisulfide. n I

12 parts of the dry, very finely'powdered partially degraded keratin(obtained as described in the preceding paragraph) are introduced atWater-bath temperature into a mixture of 80 parts of ethylpyridiniumchloride'and 40 parts of pyridine and the mixture is stirred at theaforesaid temperature until the protein has dissolvedpyridinium-chloride, the dissolving temperature must be raised to 150'to180 C.

2 Example 5 There is prepared a solution of 20 parts of linters in amixture of 200 parts of ethylpyridiumchloride and parts of pyridine. Tothis cellulose solution are added at water-bath temperature 20 parts ofthe solution of a. keratin prepared as described in Example 4, and thewhole is stirred for a short time. There is obtained a mass which iscapable of being spun and yields a fibrous material having besidesaltered physical properties, dyeinggproperties similar to those of wool.

What I claim is:-

1. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a liquefied quaternaryammonium salt obtained by addition of a halogen hydracid ester of analco- .hol containing not more than 8 carbon atoms to "a tertiary amineof the pyridine series.

2. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a liquefied quaternaryammonium salt obtained by addition of a halogen hydracid ester of analcohol containing not more than 8 carbon atoms to a tertiary amine ofthe pyridine series, the dissolution being carried out in the presenceof'a liquid base containing nitrogen whose dissociation constant'at 25C. is smaller'than 7.5 10" 3. A manufacture of solutions of proteins,this term comprising the protein-like degradation products of theproteins which still show the biuret reaction, by dissolving theproteins in a solution, in a liquid base containing nitrogen whosedissociation constant at 25 C. is smaller than '7.5 10- of a quaternaryammonium halide obtained by addition of a halogen hydracid ester of analcohol containing not more than 8 carbon atoms to a tertiary amine ofthe pyridine series.

4. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a solution, in a liquidbase containing nitrogen whose dissociation constant at 25 C. is smallerthan '7.5 10- of a quaternary ammonium halide obtained by addition of anaralkyl halide containing not more than 8 carbon atoms to pyridine.

5. A manufacture of solutions of proteins, this term comprisingtheprotein-like degradation products of the proteins which still show thebiuret reaction; by -dissolving the proteins in a solution, in pyridine,of the quaternary ammonium chloride obtained by addition ofbenzylchloride to pyridine.

6. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a solution, in a liquidbase containing nitrogen whose dissociation constant at 25 C. is smallerthan 7.5 l0- of a quaternary ammonium halide obtained by addition of analkyl halide containing at the most 5 carbon atoms topyridine.

"I. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a solution, in a tertiarybase consisting of a mixture of the technical pyridine base, of aquaternary ammonium halide obtained by addition of an alkyl halidecontaining at the most 5 carbon atoms to pyridine. V

8. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a solution, in a liquidbase containing nitrogen whose dissociation constant at 25 C. is smallerthan '7.5 10' of the quaternary ammonium chloride obtained by additionof ethyl chloride to pyridine.

9. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a solution, in pyridine,of the quaternary ammonium chloride obtained by addition 01' ethylchloride to pyridine.

10. A manufacture of solutions of proteins, this term comprising theprotein-like degradation products of the proteins which still show thebiuret reaction, by dissolving the proteins in a solution, in ammonia,of the quaternary ammonium chloride obtained by addition of ethylchloride to pyridine.

11. As composition of matter solutions containing, on the one part,quaternary ammonium salts obtained by addition of a halogen hydracidester of an alcohol containing not more than 8 carbon atoms to atertiary amine oi the pyridine series, and, on the other part, proteins,this term comprising the protein-like degradation products of theproteins which still show the biuret reaction. I

12. As composition of matter solutions of quaternary ammonium saltsobtained by addition of a halogen hydracid ester of an alcoholcontaining not more than 8 carbon atoms to a tertiary amine of, thepyridine series, and proteins, this term comprising the protein-like deradation products of the proteins which still show the biuret reaction,in liquid bases containing nitrogen whose dissociation constant at 25 issmaller than '7.5 1O- 13. Solutions of proteins, this term comprisingthe protein-like degradation products of the proteins which still showthe biuret reaction, in a solution, in a liquid base containing nitrogenwhose dissociation constant at 25 C. is smaller than 7.5 X 10- of aquaternary ammonium halide itself obtained from a tertiary base of thepyridine series and an aralkyl halide containing not more than 8 carbonatoms.

the pyridine series whose dissociation constant at 14. Solutions of anaralkyl-pyridinium halide, obtained by addition of an aralkyl halidecontaining not more than 8 carbon atoms to pyridine, and of proteins,this term comprising the proteinlike degradation products of theproteins which still show the biuret reaction, in a liquid basecontaining nitrogen whose dissociation constant at 25 C. is smaller than7.5x10- 15. Solutions of an aralkyl-pyridinium halide, obtained byaddition of an aralkyl halide containing not more than 8 carbon atoms topyridine, and of proteins, this term comprising the proteinlikedegradation products of the proteins which still show the biuretreaction, in a liquid base of v 25 C. is smaller than 'Z.5 10- 16.Solutions of an aralkyl-pyridinium halide, obtained by addition of anaralkyl halide containing not more than 8 carbon atoms to pyridine, andof proteins, this term comprising the proteinlike degradation productsof the proteins which still show the biuret reaction, in pyridine.

17. Solutions of an alkyl-pyridinium halide, obtained by addition of analkyl halide containing at the most 5 carbon atoms to pyridine, and ofproteins, this term comprising the protein-like degradation products ofthe proteins which still show the biuret reaction, in a liquid basecontaining nitrogen whose dissociation constant at 25 C. is smaller than'I.5X10- 18. Solutions of ethyl-pyridinium chloride and 01 proteins,this term comprising the protein-like degradation products of theproteins which still show the biuret reaction, in a liquid basecontaining nitrogen whose dissociation constant at 25 C. is smaller than7.5x10- 19. Solutions of ethyl-pyridinium chloride and of proteins, thisterm comprising the protein-like degradation products of the proteinswhich still show the biuret reaction, in pyridine.

20. Solutions of ethyl-pyridinium chloride and of proteins, this termcomprising the protein-like degradation products of the proteins whichstill show the biuret reaction, in ammonia.

21. Solutions of ethyl-pyridinium chloride and 120 of proteins, thisterm comprising the protein-like degradation products of the proteinswhich still show the biuret reaction, in aniline.

CHARLES GRAENACHER.

